Structure of Polymer Brushes in Cylindrical Tubes: A Molecular Dynamics Simulation

Summary: Molecular dynamics simulations of a coarse‐grained bead‐spring model of flexible macromolecules tethered with one end to the surface of a cylindrical pore are presented. Chain length N and grafting density σ are varied over a wide range and the crossover from “mushroom” to “brush” behavior is studied for three pore diameters. The monomer density profile and the distribution of the free chain ends are computed and compared to the corresponding model of polymer brushes at flat substrates. It is found that there exists a regime of N and σ for large enough pore diameter where the brush height in the pore exceeds the brush height on the flat substrate, while for large enough N and σ (and small enough pore diameters) the opposite behavior occurs, i.e. the brush is compressed by confinement. These findings are used to discuss the corresponding theories on polymer brushes at concave substrates.

Snapshot picture of a brush grafted inside of a cylinder, for , , displaying different chains in distinct colors in order to be able to distinguish them. Top shows a side view of the cylinder, and the lower part a view of the cross‐section. Note that the particles forming the cylindrical wall are not displayed.     

梳型嵌段共聚物微观相分离的耗散粒子动力学模拟

利用耗散粒子动力学(Dissipative particle dynamics, DPD)模拟方法研究了二维梳型嵌段共聚物的微观相分离, 得到了相形貌与侧链长度及链段间相互作用的依赖关系, 进一步与线型和星型嵌段共聚物微观相分离进行了对比. 模拟结果揭示了本体中影响梳形嵌段共聚物微观相分离的主要因素, 包括嵌段共聚物的组成\, 拓扑结构以及不同粒子间的排斥力.     

Effects of Electrostatic Interactions on the Translocation of Polymers Through a Narrow Pore Under Different Solvent Conditions: A Dissipative Particle Dynamics Simulation Study

Polymer translocation through a narrow pore is investigated using a particle‐based dissipative particle dynamics (DPD) method. A rigid core is included in each particle to avoid particle interpenetration problems based on the original DPD method. Electrostatic interactions of charged particles are simply represented via screened Coulombic interactions. The average translocation time τ versus polymer length N satisfies the scaling law τ ∼ N^β. The scaling exponent β depends on solvent quality. The results demonstrate that solvent quality exerts a considerable influence on the dynamics of translocation of polymers. The findings may help facilitate understanding of the dynamic behaviors of various polymer and DNA molecules during translocation processes.

     

Dissipative Particle Dynamics Simulations on the Self-Assembly of New Segmented Random-Block Copolymers in Selective Solvents

Dissipative particle dynamics simulation was applied to investigate the self-assembly of new segmented random-block copolymers (A-co-B)-b-B in selective solvents. The coarse-grained models of random-block copolymers were built. The effects of the composition of the copolymer, the interaction parameters, the volume fractions, as well as the ratio of hydrophilic particles to hydrophobic particles in the random segment, on the morphology of the aggregations were systematically investigated. The results showed that new segmented random-block copolymers (A-co-B)-b-B could self-assemble into rodlike micelle, spherical micelle and two-compartment micelle. Oval-shaped micelle and spherical micelle could be formed at different volume fractions. The simulation results provide an important reference to the design and synthesis of specific micelles.     

Core-Corona Micelles Formed by Self-Assembly of Random Copolymer and Homopolymer Mixtures: Dissipative Particle Dynamics Simulations

Dissipative particle dynamics simulation was applied to investigate the cooperative aggregation of amphiphilic random copolymer and homopolymer mixtures in selective solvents. The amphiphilic random copolymers were set to contain more hydrophilic segments. The effects of the contents of homopolymers, the chain length of amphiphilic random copolymers, the interaction parameters, as well as the simulation time, on the cooperative aggregation were systematically studied with dissipative particle dynamics simulation method. The results showed that core-corona micelles could be formed with the addition of homopolymers, where the homopolymers accumulate at the core and the amphiphilic random copolymers as the corona. This work demonstrated that the morphology and the size of the micelles could be tuned by the controlled addition of homopolymers in the process of self-assembly.     

PEO—PPO—PEO三嵌段共聚物自组装行为的耗散粒子动力学模拟

采用耗散粒子动力学方法（DPD）,模拟了聚氧乙烯-聚氧丙烯-聚氧乙烯（PEO—PPO—PEO）三嵌段共聚物在乙醇溶液中的自组装行为,考察了该共聚物的体积分数和聚氧乙烯（PEO）嵌段链长对介观形貌的影响。当F88（PEO104-PPO39-PEO104）体积分数为20％时,胶柬由初始的均衡分散态逐渐聚合,最终形成PPO为核、PEO为壳的平衡态柱状团聚体。改变共聚物的体积分数和PEO链的长度,会形成不同的介观结构,如：球状、柱状、立体网络、层状和穿孔状结构等。结果表明,DPD方法是研究三嵌段共聚物自组装行为和介观结构形成机理的有效工具,对合成具有特定结构性能的材料有一定的指导意义。     

重质油胶体聚集结构的耗散粒子动力学模拟

重质油是以沥青质为胶核分散于饱和油分中形成的极其复杂的胶体体系.本文采用耗散粒子动力学(DPD)方法研究重质油的胶体结构及其影响因素.根据重质油各组分的分子结构特征,构建了描述重质油组分的粗粒化模型化合物.模拟结果表明,本文构建的粗粒化模型能很好地反映重质油的胶体聚集结构.沥青质分子结构对胶体聚集结构有序性有显著影响,较高稠合程度的芳香环结构将使胶束结构有较高的有序性,烷基侧链则表现出分散作用.重质油中的胶质具有胶溶作用,胶质与沥青质的浓度比存在一个极限,当小于这个极限时,重质油将出现聚沉.     

Molecular Dynamics Simulations of Polymer Translocations

Summary: Molecular dynamics simulation studies of the translocation of charged homopolymers of length, N, driven by an electric potential gradient through a channel have been performed. We find that the translocation time, τ, displays an inverse power dependence on the temperature of the simulation τ ∼ (T − T₀)^−7/4, which is in very good agreement with experimental results. In addition, the dependence of τ on the driving field strength and the velocity of translocation on the polymer length N have also been obtained. The results suggest that such minimalist models are useful in modelling biological processes and that the molecular dynamics method is a suitable approach for carrying out these simulations.

Snapshot of the polymer during the simulation.     

耗散粒子动力学模拟Nafion-[Bmim][TfO]离子液体复合膜的介观结构

采用耗散粒子动力学方法模拟研究了离子液体的含量和温度对Nafion-[Bmim][TfO]离子液体复合膜的介观结构的影响。模拟发现了微相分离现象。对不同条件下的微相分离形成的孔径分析表明,随着离子液体在复合膜中含量的增加,离子液体在膜中的聚集状态由分散的团簇转变为连续的通道,但过高的含量会产生腔室结构。随着温度的上升,离子液体通道的结构变得更加复杂,原有的腔室结构转化为通道的新支路,即高温下离子液体通道变得更加连通。界面分布几率和径向分布函数的计算结果表明,离子液体的阳离子烷基链嵌进Nafion主链中,侧链磺酸基团分布的变化直接影响咪唑基团和阴离子在微相界面的分布。本工作在介观水平上探索了Nafion-离子液体复合膜结构,可为开发高温聚电解质燃料电池材料提供一定的参考。     

Dissipative Particle Dynamics Simulations to Investigate Aggregation of Peptide Amphiphile Nanofibers

Dissipative Particle Dynamics (DPD) method was carried out to investigate the self‐assembly phase behavior of peptide amphiphile (PA) molecules. The simulations showed that these molecules were self‐assembled into three‐dimensional fiber‐like cylindrical aggregates by the assistance of water solvent. The results of DPD simulation are sensitive to various factors including the size of solvent bead, temperature, and the bead ratio of PA to solvent. We found that using 5 to 9 water cluster and solvent bead gives a result of the aggregation of PA molecules into cylindrical fibers. The criteria of forming nanofibers are bead ratios of PA to water larger than 1:6 and temperature above 340 K. The estimated diameter of the cylindrical aggregate agrees well with the experimentally measured value.     

Dissipative Particle Dynamics Models of Orientation of Weakly‐Interacting Anisometric Silicate Particles in Polymer Melts under Shear Flow: Comparison with the Standard Orientation Models

Dissipative particle dynamics (DPD) models of orientation of weakly‐interacting silicate particles in a polymer matrix are presented. To examine the DPD models, the evolution of orientation under shear flow is compared with the predictions of the standard orientation models, namely, the Folgar–Tucker (FT) and the strain reduction factor (SRF) models. While the orientation patterns are the same in all models, the slow orientation kinetics observed in previous experiments is only predicted in the DPD and SRF models. Since the coefficients of the SRF model are in good agreement with the experiments, the good tally between the DPD and SRF models supports the capability of DPD to successfully simulate the orientation process. The orientation in a large cell constructed from unit cells with various averaged initial orientation angles is evaluated from evolutions in the unit cells based on the affine deformation assumption. The good agreement between such calculations and SRF model predictions supports that the affine deformation assumption in the large cell is reasonable. It is argued that the nonaffine deformation originated from the particle‐based nature of DPD models at the lower scale could be combined with the affine deformation at the upper scale to yield appropriate estimations of the orientation state.

     

梳状-线性共聚物自组装的耗散粒子动力学模拟

梳状-线性共聚物在选择性溶剂中可以自组装形成两种不同类型的聚集体, 其中第I类的自组装发生在亲、疏溶剂链之间, 而第II类发生在线性链和梳状亚结构之间. 本工作利用耗散粒子动力学方法, 分别研究了梳状-线性共聚物在侧链和主链选择性溶剂中形成的这两类聚集体, 探讨了侧链长度和侧链数量等对聚集体类型及形貌的影响. 研究表明, 第II类聚集体在侧链长度较短且侧链数量较多时容易形成. 将模拟结果与文献报道的实验结果相比较, 发现两者能较好地吻合. 此外, 本研究获得了一些在实验中较难得到的信息, 有助于进一步理解梳状-线性共聚物的自组装行为.     

Multicompartment Micellar Solutions in Shear: A Dissipative Particle Dynamics Study

Summary: Dissipative particle dynamics simulations were performed to study the effect of shear on the rheological behavior of multicompartment micellar solutions, demonstrating that both shear thickening and thinning can occur, and the macroscopic behavior was elucidated at a molecular level. In addition, a novel shear‐induced morphology of “sphere‐on‐rod” was observed. This work provides useful information towards a complete understanding of the properties and morphologies of multicompartment micelles that is useful for future rational synthesis of novel micelles.

Shear‐induced morphological transitions and rheological behavior in multicompartment micellar solutions formed from star triblock copolymers.     

Microphase Separation of Phenylene Oligomers with Polymeric Side Chains: A Dissipative Particle Dynamics Study

The microphase‐separated morphologies of p‐phenylene oligomers with POx, PCL, PS, and PEO side chains are studied using DPD simulations. It is shown that the microphase‐separated morphologies depend significantly on the degree of chemical incompatibility between the components as indicated by the Flory‐Huggins interaction parameters. The good agreement of the microphase separated morphologies as simulated by DPD with the experimentally determined thin film morphologies suggests that DPD can produce convincing morphological information at the nanoscale. The results show that grafting of polymeric side chains can be an important tool to control the morphology of polymers with a rigid backbone.

     

遥爪型聚合物交联反应的耗散粒子动力学模拟

利用耗散粒子动力学(Dissipative particle dynamics, DPD)方法研究了稀溶液中遥爪型聚合物的交联反应过程. 考察了体系中交联度、 链长及浓度等因素对反应达到稳态时所形成的网络结构的影响, 并通过计算聚合物交联结合能(U), 统计达到稳态时特征交联结构的数量来判定各因素对体系的作用. 结果表明, 交联度决定体系的微观结构, 而聚合物链长决定交联结构的连通性. 另外, 特征环形结构数与遥爪型聚合物的浓度及链长均存在线性依赖关系.     

Self-Assembly Behaviors of Heterogemini Surfactant in Aqueous Solution Investigated by Dissipative Particle Dynamics

As a preliminary study, self-assembly behaviors of heterogemini surfactant in aqueous solution are explored tentatively by means of dissipative particle dynamics simulation. Five kinds of heterogemini molecules are involved, and a variety of novel morphologies have been obtained. Results based on detailed comparisons among themselves and with traditional symmetric gemini surfactant show the proportion of hydrophilic to hydrophobic chain lengths in one monomer is the most important, more difference between proportions in the two monomers can induce more diverse self-assembly morphologies. The second important is the hydrophilic chain length, in which a small change can lead to obvious difference in self-assembly behaviors. While the length of hydrophobic chain has a less important influence, only the concentration for self-assembly morphologies appearing can be affected by its change. The microscopic morphology of heterogemini surfactant in its self-assembly structure can be embodied through its radius of gyration. Our simulation results can undoubtedly provide a theoretical guide to further research towards self-assembly behaviors of heterogemini surfactants and practical applications of these matters.     

耗散粒子动力学和纳维边界条件在微米纳米流体力学模拟中的应用

耗散粒子动力学是一种粗粒化的计算模拟方法,在微米和纳米流体力学中有着广泛的应用.由于界面在微小体积流体中的重要性,边界条件的选取在微米和纳米流体的研究中起到了关键性的作用.我们简单地介绍了耗散粒子动力学的模拟方法,并以此为基础,介绍了能够实现纳维边界条件的可调滑移长度的边界条件模拟方法.通过条纹状图案修饰的超疏水表面的流体力学行为研究,和高分子链在微米纳米流体器件中的运动研究2个例子,耗散粒子动力学结合纳维边界条件的模拟方法的实用性和可靠性得到了证实.     

Phase Behavior of Amphiphilic Molecules in the Presence of One Solvent: A Dissipative Particle Dynamics Study

We simulate the phase behavior of amphiphilic molecules in the presence of one solvent by DPD. In general, DPD has successfully captured most of the effects of composition of amphiphilic molecules, solvent selectivity, and solvent amount, on the phase transition behavior obtained by both SCMF calculations and experiments. When a neutral good solvent is added, the solutions undergo a lyotropic transition analogous to the thermotropic transition in the melts. Furthermore, the order‐disorder transition results obtained via DPD are in good agreement with theoretical predictions by including the fluctuation effects, as well as with experiments. In the selective solvents, various transitions from the “normal” phases (i.e., the minority blocks form the minor domains) to even the “inverted” phases (formed by the majority blocks) have been observed by varying solvent selectivity and solvent amount. Since the packing order of the spheres is greatly affected by the finite size of the simulation box, it becomes difficult to examine the most stable packing array of spheres via DPD as has been predicted by SCMF theory. However, DPD reveals a possible spherical order of A15, which has been ignored in current SCMF work but observed in some amphiphilic molecule systems.